Process for breaking petroleum emulsions employing certain amine-modified thermoplastic phenol-aldehyde resin salts



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Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 2, 1953,

Serial No. 329,485

18 Claims. (Cl. 252-341) The present invention is a continuation-in-part of my two co-pending applications, Serial No. 288,745, filed May 19, 1952, now abandoned, and Serial No. 296,086, filed June 27, 1952, now U. S. Patent 2,679,487.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil," roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which .constitutes the continuous phase of the emulsion.

It also provides an economical rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value inremoving impurities, particularly inorganic salts, from ,pipeline oil.

My aforementioned co-pending application, Serial No. 296,086, filed June 27, 1952, is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a'demulsifier including condensation products of certain phenol-aldehyde resins, certain basic hydroxylated polyamines and formaldehyde thereindescribed.

My present invention is concerned with demulsification which involves the use of the aforementioned amino resin condensate in the form of a gluconic acid salt, -i. e., a form in which all or part of the basic nitrogen atoms .are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

Needless to say, all that is required is to prepare the amine resin condensates in the manner described in the two aforementioned co-pending applications, and thenneutralize With gluconic acid which, for practical purposes is as simple as analogous inorganic reactions. 1

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions ofthe water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have suflicient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a Water-insoluble solvent, generally xylene,.is described as an index of surface activity.

The present invention involves the surface-activityof the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily'be xylene-soluble. Ifsuch compounds are not Xylene-soluble the obvious chemical equivalent or equivalent chemical test can bemade by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal rates Patent weight of Xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. ence in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For convenience, what is said, hereinafter will be divided into six parts: I

Part 1 is concerned with the general structure of' the amine-modified resins which are converted into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondary polyarnines which may be employed in the 7 preparation of the herein described amine-modified resins; Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds which are neutralized subsequentlywi-th gluconic acid;

Part 5 is concerned, with the conversion of the basic condensate into the corresponding salt of gluconicyacid; Part6 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reactionprod- V inwhich R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atorns but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. j In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure-is derived from a hydroxylated basic polyamine and usually a strongly basic polyamine having at least one secondary amino radical and free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be indicated 2 RI HN in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, .arylalkyl radical, etc.,

with the proviso that at least one occurrence of R contains an amino radical which is not "part of a primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical, and with the further proviso that there be present at least one hydroxylated hydrocarbon radical such as a hydroxyl alkyl radical, a hydroxy alicyclic-radical, a-hydroxyalky l- Patented Nov. 20, 1956 It is understood the referaryl radical, etc. Such hydroxylated radical need not be limited to a single hydroxyl group as in the case of an alkanol radical but may include 2 or more hydroxyl groups, such as a glycerol derivative or, in essence. a dihydroxy propyl group.

Actually, what has been depicted in the formula above isonly an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to oxyalkylated derivatives obtained by the oxyethylation or oxypropylation, for example, of substituted polyalkylene amines of the following structure:

in which R has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generallyfrom 1 to 3,'with the proviso that the other previoulystat'ed requirementsare met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair. Reaction with an alkylene oxide, such as ethylene oxide or propylene oxide must of course be sure that the derivative so obtained still 'has at least one secondary amino hydrogen group, all-of which will be illustrated by numerous examples subsequently.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al., which describes alkylene di amines and polymethylene diamines having the formula where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integerlfsuch as l to 8. Such compound as the one just described can be reacted with a single mole of ethylene oxideor 'propylene oxide or glycide to give a suitable reactant. 1

-A further limitation in light of the required basicity isthat the secondary amino radical shall not be directly joined to an aryl radical or acyl radical or some other negative radical. Needless to say, what has been stated above in regard to the groups attached to nitrogen is not intended to exclude an oxygen-interrupted carbon atonrlinkage-or a-ring linkage as in the instance of compounds obtained by converting an N-aminoalkylmorpholine of the formula wherein n-is, a whole number from. 2 to 12 inclusive,

4 and the nitrogen atoms are separated by at least two carbon atoms, into a secondary amine by means of an alkylene oxide, such as ethylene oxide, propylene oxide, or glycide, so as to yield a compound such as The introduction of two such hydroxylated polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counter-balancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another efiect is introduced, particularly another hydrophile efiect. In the present procedure the polyamino reactant invariably has at least one hydroxyl group and also may have a reoccurring ether linkage, all of which in turn affects the hydrophile properties.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending onthe procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a non-oxygenated hydrocarbon solvent, such as benzene or xylene. The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insolublestage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact. one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline 'catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is stillimportant from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed inpreparing the compounds described subsequently in detail, there is no objection to the employing Jof a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150 C.

What is said above deserves furflaer amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind 'herein described will begin at least at comparatively low temperatures, forinstance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of'higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive; Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way ofexplanation to avoid any limitation in regard to the appended claims.

PART 2 no Q l l...

In the-aboveformula n represents a small Whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resin herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic non-hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic polyamine may be designated thus:

RI HN subject to what has been said previously as to the presence of at least more than one amine radical in at least one occurrence of R with the proviso, as previously stated, that the amine radical be other than a primary amine radical, a substituted imidazoline radical or a substituted tetrahydropyrimidine radical, with the proviso that there must be present at least one hydroxyl radical as part of at least one of the occurrences of R. However, if one attempts to incorporate into the formula a structure such as an oxyethylated or oxypropylatedde- "7 rivative of a substituted polyalkyleneamine of the following type:

in which the various characters have the same significance as in initial presentation of this formula, then one becomes involved in added difficulties in presenting an overall picture. Thus, for sake of simplicity, the hydroxylated polyamine will be depicted as subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction products, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R R inl-which R"' is-the divalent radical obtained from the particular aldehyde employed to form the resin. For

reasons which are obvious the condensation product ob tained appears to be described best in terms of the method of manufacture. i

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst,

such strong acid should be neutralized. Similarly, if a 7 strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units,

or just 6'units, etc. It is usually a mixture; for instance,

TABLE I Mol. wt Ex- R of resin ample R Position derived 'n molecule number of R om (based on n+2) 1a Phenyl 3. 992. 5

2a Tertiary butyl 3. 882. 5 Secondary butyl. 3. 882.5 Cyclo-hexyl. 3. 1, 025. 5 Tertiary amyl d 3. 959. 5 Mixed secondary 3. 805.5

and tertiary amyl. Propyl 3. 805. 5 Tertiary h 3. 1, 036. 5 0ctyl 3. 1, 190.5 Nonyl 3. 1, 267. 5 Decyl--. 3. 1, 344. 5 Dodec 3. 1, 498. 5 Tertiary butyl 3. 9.

Tertiary amyl 3. 1, 022. Non 3. 1, 330. Tertiary butyl 3. 1, 071.

Tertiary amyl 3. 1, 1 Nonyl 3. 1, Tertiary butyl Propional- 3. 1,

dehyde. Tertiary amyl 1, N 1,

on Tertiary butyl Tertiary amyl Nonyl Tertiary butyl Tertiary arnyl Nonyl Tertiary amyl Hexyl Cyclo-hexyl agar-tat ondary amino radical, free from primary amino groups,

free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, Whether monovalent or divalent, are 1 alkyl, 'alicyclic, arylalkyl, or heterocyclic in character, subject of course to the. inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been. made to a number of polyamines which are satisfactory: for -use as reactants in the instant :condensation procedure. They can be obtained by hydroxyalkylation of low cost polyamines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines gherqmay be as-rnanyas 5, 6 or7 nitrogen atoms. .Such

amines. are susceptible to terminal alkylation or the equivalent ,i. e reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case .of polyamines having at least 3 nitrogen atoms-or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. the same Way, the polyamines can be subjectedto hydroxyalkylation by reaction with ethylene oxide, propylene .oxide,,glycide,. etc. In some instances, depending on the structure, both types of reaction may be employed, i. e.,, one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of examplethe following formulas are included. It will he noted they include. such polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the, like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

CzHt on3 vHO C2115 Jolene qa der-si c aesthxis sxidarb a yleg 'aaids or eslys dsz Mh ha r ss ld-P YlQll 1 -P 1 b ri vst as alz ir a t on r-i v v n a con a l am neas aa e qn al y l fam n s c a 1 ib l m n iky lib y ,aririne, dicyclohexylamine, or -mixed ,arnineswi' imine .so as ,to. introduce a primary aminmgrQQP r hich i b asts wi am l l x de l wsirb rea .tion, with animineand then ,theuseofan alkylenepxide .asa l im r wm s a wit an introduce two molesof analkyleneomde, compound comparable to ethyl diethanolarn i v V w th w mo e o a mi .and.th .wit lwp t ad s of ,ethylenepxide. A

Re actions involving the same re actants previously described, i. e., a suitable secondary monoamine plus an aikylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine Land plus the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In thecaseof primaryamines one can either employ two moles of an alkyl ene oxide so'as' to convert both amino-hydrogen atoms into an alkanol group, or'the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile effect by virtue .of .thetether linkage. Suitable polyether amines-suscep- .tibleto conversionin the manner .described include-those ofthe :formula l-Rflw e in which x is a small whole number having avalue of l or more, and may be as much as 10 or 12; n is an integer having a valueof 2 to 4, inclusive; m represents the numeral l to 2; and m representsanumber 0 to 1, with the proviso thatthe sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. i r

The preparation of such amineshas. been described in the literature and particularly in two United states patents, to'wit, U. S. Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,137, dated August 8,1944, to Spence. li 'l te n ist td s alq lk r hsfif v NB RO(CHz)a as described in U. S. Patent No. 2,375,659, dated May 8,

imet ts Pt PYL;am l ty ie s 1945, to Jones et al. In the aboveiormulmk may be Other suitable secondary amines which can be convert ed into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma -phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion intopolyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such presentation is an oversimplification. It was pointed out that at least one oc- CH3 CH3 H NpropyleneNpropyleneN CaHtOH CHa N C zH g C flHlg C zHtN C aHiN HOCzHt -In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines 'with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two difierent structuresfor the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to suchmultiplicity of reactive radicals. This can be illustrated by the following formula v v Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactcation, it is diflicult to actually'depictthe final product.

12 ant used for the instant condensation reaction may be illustrated by the following additional examples:

\v-omom-rt-cmcm-orr H a HOCH CH1NH-CHgCH NHCH CH OE OH OH HocmdrtoumHcH,0H,-NHcH, JHoH,oH H0CE'2OH|NHCH:

As is well known one can prepare ether amino alcohols of the type RO-CH2CH 0H) CHzNHCHzCHeNHCH CH (OH) CH2OR a number of suitable amines are included in subsequent Table II.

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, al

though it may be so illustrated in an'idealized simplifiof the cogeneric mixture except in terms of the process move the excess xylene.

13 itself. The condensation of the resin, the amineand formaldehyde is-described in'detail in applicationsSerial Nos. 288,745 and 296,086, and reference is 'made to-those applications for a discussion of the factors involved.

.14 dark red in color and had the consistency of a StiCkYnflllld orta ckyresin. ,The overall time for reaction was s omewhat under 30 hours. In other examples it varied from 24 .to morethan 36 hours. The time can be-reduced by cutting the lowtemperature period to approximately a Little more need be said as to the actual procedure 3 to 6 hours. Note that in Table II following there are employed for the preparation of the herein described a large number of added examples illustrating the same condensation products. .The following example will serve procedure. In each case .the initial mixture was stirred by way of illustration: and held at a fairly low temperature (30 to 40 C.) Exam 18 1b for a period of several hours. Then refluxing was emp ployed until the odor of formaldehyde disappeared. The pheneol-aldehyde resin is-the one'that has-been After the odor of formaldehyde disappeared the phaseidentified previously as Example 2a. It was .obtained separating trap was employed to separate out all the wafrom a para-tertiary butylphenol and formaldehyde. ter, both the solution.andcondensation. After all the The resin was prepared using an acid catalyst which was water had been separated enough xylene was taken out completelyneutralized at the end of the reaction. The to have-the finalproduct reflux for several hours-some- -molecular weight of the resin was 882.5. This correwhere in the range of l45- to -l50-'C., or thereabouts. sponded to an average of about 3 /2 phenolic nuclei as Usually the mixture yielded a clear solution by the-time the value for n which excludes the 2 external nuclei, i. e., the bulk of the water, orall of the water, had been-rethe resin was largely a mixture having 3 nuclei and 4 moved. nuclei, excluding the-2 external nuclei, or 5 and 6 over- Note that as pointed out previously,-'this procedure is all nuclei. The resin so obtained in a neutralstate had illustrated by 24 examples in Table II.

TABLE 11 2 Strength of Reac- Beac- Max.

Ex. Resin Amtx, Amine used and amount formalde- Solvent used tion tion distill. N0, d grs hyde soln. and amt. temp, time, temp,

and amt. 0. hrs. C.

882 Amine A, 296 g 30%, 200 g... Xylene, 5 00 21-24 24 150 480 Amine A, 148 g 37%; 81 g Xylene 4 1) gm. -20-23 7 27 156 633 do ;.do Xylene, 610 g 22-27 I142 441 Amine B, 176g 100 xyl n aoo '20-25 28 145 430 do 37% 81 Xylene, 425 g 23-27 34 r 150 533 dn Xylene, 500 25-27 152 882 Amine o, 324 g Xylene, 625 gm. 23-25 as 141 480 Amine c, 162 g Xylen -315 g 20-21 2s 114s 633 do Xylene, 535 gr. 23-24 25 .140 473 Amine D, 256 g ,Xylene, 425 2.. 22-25 25 148 511 dn -Xy'lene, 450 g -20-21 25 .158 665 dn .do Xylene, 525 g 21-25 28 .152 441 Amine E, 208 g 37%, 81 g Xyleue, 400 g 22-24 26 143 430 do do do 25-27 36 .144 595 do Xylene, 500 g 26-27 34 141 441 Amine F, 236g Xy1e11e,'400 g 21-23 25 153 480 n on 20-22 22 .150 511 an Xylene, 500 gm- 23-25 27 155 542 Amine G, 172 g Xylene, 450 20-24 36 152 547 Amine H, 221 g Xylene, 500 g 20-22 30 ;-148 441 do Xylene, 400 gm- 20-29 24 143 595 Amine 1,172 g Xylene,-450 g 20-22 -32 -151 391 Amine I, 86g 30%,50 g..- Xylene,300 g 20-26 -36 .147

V a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl) ethylenediamine were added. The

and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part of the xylene was removed until the temperature reached approximately 150 C. or perhaps a little higher.

The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to re- The residual material was As to the formulas of the above amines referred to as ,Amine A through Aminel, inclusive, see immediately following:

' funnel.

HO CHaCHzNH-CH:

HO CH2CH2NH--CH HO CHaCHrNH-CH:

Amine H- PART 5 Amine I- The conversion of the basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensates invariably contain more than two basic nitrogen atoms. One can neutralize either one, or more, or all basic nitrogen atoms.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, at least not of the salts of the herein described condensates. Such salts appear to be stable, or stable for all practical purposes, at temperatures slightly above the boiling point of water and perhaps at temperatures as high as 150 C. or thereabouts.

For reasons pointed out previously, it is most convenient to handle the condensate as a solution, generally a solution in an inexpensive solvent, such as benzene, xylene, an aromatic petroleum solvent, or the like. A number of the condensates previously described have been prepared in 50% solution as noted. Adding the calculated stoichiometric amount of 50% gluconic acid, calculated on the basis of the theoretical basic nitrogen atoms present, forms such salt which, in many instances may be slightly on the basic side and in other instances perhaps slightly on the acid side. The salt formation is merely a matter of agitating at room temperature, or:

somewhat higher temperature if desired, particularly under a reflux condenser. I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on the composition, there is some separation of an aqueous phase. On a laboratory scale, this procedure is conducted in a separatory If there is separation of an aqueous phase, the aqueous phase is discarded and the solution can be brought back to a predetermined concentration by the addition of a hydrocarbon solvent, such as xylene, or by the addition of an alcohol, such as methyl, ethyl or propyl alcohol; or, if need be, one can employ a bridge solvent having hydrotropic properties in case of the diethylether of ethyleneglycol, or similar solvents.

The gluconic salts can be obtained in non-aqueous solution by using a slightly modified procedure. The procedure depends on the fact that the phase-separating trap can be used but it is preferable to stay below 150 C. so as to avoid any possible decomposition.

The xylene solution of the condensate, as previously described, is subjected to vacuum distillation so as to remove about one-half the xylene. Approximately twothirds of the xylene removed is replaced by benzene. This mixed solvent combination is subjected to refluxing action under a condenser with a phase-separating trap. With the distillation point adjusted so as to be somewhere between 110 to 135 C. the mixture is refluxed and the water separated. If it is not within this range more benzene is added or, if need be, a little more xylene is added to bring it within the range. By this method the phase-separating trap eliminates the water. The temperature at all times is left below 140 C. At the end of the separation a suitable amount of solvent is added, or

After salt formation is complete, 'jj

i6 eliminated, by distillation so as to yield a solution of predetermined concentration, for instance, 50%.

Using a somewhat similar procedure one can obtain the solvent-free material by merely subjecting the xylene solution of the condensate to vacuum distillation so as to remove all the xylene. The condensate itself is per-, fectly stable at 150 C. or thereabouts and, thus, there is no particular danger of degradation involved in this step. The solvent-free material is then dissolved in benzene instead of xylene and water eliminated in the manner previously described. The benzene is eliminated by vacuum distillation in such a way that the temperature never gets above C. or C. Actually, with care the solution previously described, to wit, the xylenebenzene solution, also can be removed without decom position.

An examination of the hydroxylated polyamines employed as reactants, and with particular reference to some of the indicated types previously described, emphasizes the fact that the condensate may have present secondary amino radicals, and invariably has present hydroxyl radicals attached to a nitrogen atom, such as an ethanol radical or the like. When such products are neutralized, particularly when neutralization is complete, it becomes apparent that one has a material which, in one way, is analogous to triethanolamine oleate; or, for that matter, triethanolamine gluconate. In another way the analogy is similar to diethanolamine oleate or diethanolamine gluconate. If triethanolamine oleate is heated it can be converted into oleyl triethanolamine, i. e., involving an ester linkage. Similarly, if diethanolamine oleate is heated one can form the corresponding amide or perhaps,

under certain conditions, the corresponding ester. Obviously, esters can invariably and inevitably form in regard to the completely neutralized product and even in some cases in regard to the partially neutralized product. This is, of course, assuming that appropriate conditions of reaction are selected. In other instances where there is a residual secondary amine radical one may form amides or, for that matter, mixtures of both amides and esters. For this reason previous reference to decomposition must be construed to mean not only decomposition in the sense that degradation or inner ethers are formed, but also in the sense that an entirely new and valuable compound, or compounds, may be formed. Such reactions, of course, form wateras a by-product regardless of whether amidification or esterification is involved.

Exa mple 1c This salt was made from condensate Example 1b. Example 1b, in turn, was made from resin 2a and symmetrical di(hydroxyethyl)ethylene diamine, previously referred to as Amine A in the notesfollowing Table II. 882 grams of the resin were dissolved in an equal weight of xylene and reacted with 296 grams of the hydroxylated diamine previously described, and 200 grams of 30% formaldehyde. All this has been described previously. The, weight of the condensate on a solvent-free basis was 1202 grams. This represented approximately 28 grams of basic nitrogen. To this mixture, with constant stirring, there was added 785 grams of gluconic acid. This solution waspoured into a separatory funnel or syphon arrangement and allowed to stand at 45 C. for IV: days.

There was no separation of any kind. Purely as a matter of precaution to prevent subsequent turbidity 100 grams of isopropyl alcohol were added and enough xylene to bring the final product just short of 3200 grams, or, more exactly, 3189 grams. This represented approximately a 50% solution.

A number of other examples are included in Table III, following.

TABLE III Condensate in turn derived from Salt formation Salt Salt from Wt. of Final ex. con- Amt. 37% conden- Theo- 50% wt. ad- No. den- Resin Amt. sol- Amlne rmsate on retical glujusted to sate No. resin, Solvent vent, Amine used 1 used, aldesolventbasic conic approx. No. gms. gms. gtns. hyde, free nitroacid, 50% salt, gms. basis, gen, gms. 50% so1v.,

gms. gms. gms.

480 148 81 640 28 785 2, 065 633 148 81 793 28 785 2, 371 441 176 I 100 629 28 785 2, 043 480 176 81 868 28 785 2, 521 633 176 100 S51 28 785 2, 487 480 162 2 100 654 28 785 2, 093 633 162 2 100 807 28 785 2, 399 473 256 100 741 28 785 2, 267 511 256 3 100 779 28 785 2, 343 665 256 100 933 28 785 2, 651 13c 882 296 2 200 1, 202 28 392 2, 796 14c 441 176 2 100 629 28 392 1, 650 15c 882 625 Amine C 324 162 l, 230 28 392 2, 852

1 For description of amines see notes following Table II. 1 30% formaldehyde.

PART 6 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of l to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Gluconic acid salt, for example, the product of Example lc,

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described my invention what I claim as new and desire to secure by Letters Patent, is:

l, A process for breaking petroleum emulsions of the water-in-oii type characterized by subjecting the emulsion to the action of a demulsifier including the g onic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 cuie; said resin being difunctional only in regard to niethylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula polypropylated napthalene petroleum solvent, 15%;

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyarnine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the fur the: proviso that the polyamine be free from any priiary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted. at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resi nous condensation product resulting from the process be heat-stable.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, Waterinsoluble, low-stage phenol-aldehyde resin having an and not over 6 phenolic nuclei per resin mole-t average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and sub stituted in the 2,4,6 position; (b) a basic hydroxylated polyatnine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sutliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable.

4. A process for breaking petroleum emulsions of the tivity; said resin being derived by reaction between at difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group,

and having not over 32 carbon atoms in any radical attached to any amino nitrogen atoms, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further provisio that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and

with the final proviso that the resinous condensation product resulting from the process be heat-stable.

S. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterv insoluble, low stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula.

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the fur ther proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrirnidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and re:

sultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable.

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; wtih the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and sub stituted in the 2, 4, 6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensationreaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable.

9. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the gluconic acid salts of the basic products obtained in turn in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the para position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable.

10. The process of claim 1 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

11. The process of claim 2 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

12. The process of claim 3 withthe proviso that.the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 4 with the proviso that the hydrophile properties of the gluconic acid salt of the basic produce in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water. l4. The process of claim 5 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water. i

15. The process of claimv 6 with the proviso that the hydrophile properties of the gluconic acid salt of the" basic product in an equal weight of xylene are suflicientl to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 7 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken' vigorously with l to 3 volumes of water.

17. The process of claim 8 with the proviso that the. i hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are suflicient to produce an emulsion when said Xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 9 with the proviso that the hydrophile properties of the gluconic acid salt of the basic product in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken' vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS De Groote May 25, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE GLUCONIC ACID SALTS OF THE BASIC PRODUCTS OBTAINED IN TURN IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 